TW455625B - Fluorescent polymers and a method of preparing the same - Google Patents

Abstract

Disclosed are a fluorescent polymers and a method of preparing the fluorescent polymer, comprising copolymerizing one or more ethylenically unsaturated monomers with a fluorescent compound in the amount of 0.001 to 3.0 wt% based on the total weight of the monomers; wherein the resultant polymer contains a fluorescent group, and the florescent compound is selected from the group consisting of naphthalene, anthracene, phenanthrene, fluoranthene, acridine, carbazole, pyrene, chrysene, triphenylene, and perylene, and their substituted aromatic derivatives.

Description

^ 55625 A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs. 5. Description of the Invention (1) 1 | Invention Back 1 1 1 The present invention relates to a method for preparing a fluorescent polymer and contains the fluorescent * I Photometric Polymer coating composition 〇 Especially t This method is related to the preparation of m 1 Please 1 I Polymers that can be used in coating composition 9 Contains human fluorescent compounds > As a result of reading 1 1 | The method of preparing fluorescent polymers by detecting 0 to 1 by fluorescence method is disclosed in US 5.125, 9 2 9 (Α π gy), meaning 1 thing [Among them, Michael icba el) addition reaction can be Fluorescent t-originated amine-based term and 1 acid polymer are obtained. In this case, f fluorescence is generated by the main polymer of the polymer. Page 1 Due to its chemical properties, moreover »Most of them produced by Michael addition reaction-> 1 polymer will not have fluorescence ΰ 1 US5, 0 4 3, 4 0 6 ( F 0ng) reveals-a kind of copolymerization of acrylamide monomer with a monomer containing 1 1 side fluorescein »And in the acrylamide polymer content and order 1 into the fluorescent part Method 0 The main limitation of this method is the lack of monomers that can provide commercially available 1 | side m fluorescent part 0 even if other monomers can be modified and merged with 1 I side fluorescent part, but this move Will increase the cost to increase the production cost of this fluorescent polymer] 1 σ 1 Two methods disclosed by A η ey and Fo ng t According to the chemical properties 1 involved or from the lack of available Fluorescent Starter 1 requires 1 1 C for its usability and is therefore required. It can be used in a wide variety of polymers and has a fluorescent property. 9 Therefore, 1 1 can be used more widely in this kind of fluorescent polymer. II. Invention 1 1 The first specific example of the present invention includes M types of fluorescent light. -1 1 | Method > includes copolymerizing one or more ethylenically unsaturated monomers with a fluorescent compound of a selective polynuclear aromatic 1 1 hydrocarbon and a substituted aromatic derivative thereof, wherein 1 1 This paper size applies to the Chinese national standard (CNS) Liushuangjiange (2IOX297 mm) 3 9 14 0 2 4 5 5625 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) 1 1 Contains a fluorescent group 0 1 1 | The second specific example of the present invention is related to a 1 1 coating composition having enhanced IJ V gate durability. The coating composition t includes ethylenically unsaturated mono 91 and polynuclear aromatic hydrocarbons. 1 I Poem 1 Fluorescent compounds of type I and their substituted aromatic derivatives, and side-m photon first 1 | Read 1 I m-polymerization of ethylenically unsaturated monomers with functional m 1 | 1 〇 Note Xuan 1 | The third specific example of the present invention is a method for identifying and quantifying the content of the fluorescent polymer (if any) contained in the coating. Item T This method includes steps m is% of this equipment |; (a) obtain the coating composition to be tested or a sample of the obtained coating; (b) detect the fluorescence, ^ 1 1 measure the fluorescence r and (C) measure the fluorescence contained in the sample Intensity of fluorescent polymer wavelength 1 Ⅱ JL m-order I The following terms used in this specification have the following definitions t Unless the text clearly indicates otherwise 1 1 I "latex" or "latex composition" It means that the water-insoluble polymer can be prepared by the conventional polymerization 1 I reaction technology, such as emulsion polymerization, 1 1 liquid 0 "latex h. It also means the polymer t dispersed in the aqueous composition, where the i polymer can be directly used in Preparation in aqueous medium »or 1 1 preparation before non-aqueous medium (such as β blue for solution polymerization), then m and then dispersed in aqueous medium to prepare 1 1 preparation 0" fluorescence "or" fluorescence " ; Means that when excited by radiation, the compound can occupy a second excited state of 1 1 m “fluorescence” or a compound that can emit 1 radiation at a lower energy than the original excited state 0 ”chromophore” means Fluorescent compound covalently linked to polymer 1 I. "Main 鐽" means polymer 1 I main 除 t " side 鐽 "except white side chain or end group M means white polymer main 鐽 m pendant group * And "end group" table Shows 1 t dangling base from the polymer m-terminus 0 Reference paint used "P VC" means pigment 1 i This paper size is applicable to Chinese national standards (CNS > Λ4 current grid (210X297 mm) 4 9 1402 Λ5 56 2 5 A7 B7 5. Description of the invention (3) Body stain concentration. The words "basic" and "partial" can be used interchangeably and use the following to write centimeters and nanometers ¾ Fan Zhiding-So ο ο Clearly say that the nature is fixed to live 1 = there is another S non Ms Xi Zi ' -> Analyze the number of UV readings in the reading layer. The fatigue pressure is high. The suppression should be anti-agglomeration. The 0 can be used to suppress the reaction. Affinity is weak. The agent will be used to suppress the reaction, and the reaction should be equal to the reaction of the polymer. The advancement of the bases, the clutches, the clutches, and the swimmers should be promoted. Fang 47 Nuoliduo is designed for the country 1) Russia 96 points (1 is η See the example of η 可 圑 圑 发 发 烃 烃 烃 烃 芳 芳 芳 芳 芳 多种 多种 多种 a variety of subjects in this period 及 d and used to suppress anti-reunion polymerization The family fragrant M is also used to make the formula fragrant fang. This loss of M 0 can also be derived from the generation of derivatized hydrocarbons, aromatic fragrant and nucleus, and many of its hydrocarbons are fragrant nucleus of the family. This 〇 物 合 化 限 not only (#Read the back of the first> .i 意 事 ^ (Fill on this page again)-Packing. Ordered aryl or alkyl-containing alkyl radicals are taken directly or the branched acid is used to obtain sulfonates. * The original heteroester 0 meaning and any kind: acid 丨 carboxylate Health, Yanqi, and Naphthalene: Cyanocyanine, β β-containing encapsulations, Hydrocarbon family, Fangcai Erduo Zhizhi, Jiazolium 0, Sumidazine, and Acryl β benzene Benzophthalene printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The product is printed with naphthalene, which is used as a bio-derived aromatic compound. It can be used to make the official combination of light and other drugs. It can be used to gather other fluorescein. It can also be used to make things fluorescent, and it is also suitable for the single-aromatics of Yanzhong-body family. Take one note and make another. Borrow its memorandum, and use the dart as an example of the rest of the book. 、 Distinguished objects have been obtained by the 1st place or the material group ο The coating pairs are made by the system of poly M. And the polymer polymerization and copolymerization properties of single light and fluorescent are not the same as those of paper. Standard (CNS) 8 4 mud grids (210X25I7 mm > 9 1402 455625 A7 B7 Printing by the Central Standards Bureau of the Ministry of Economy, Shellfish Consumer Cooperative, Co., Ltd. V. Description of the invention (4) Coating) Coating sampling,-I analyze the sample to determine Fluorescence wavelength and fluorescence emission intensity can be completed. 0 LC P LC or GFC can be used to determine whether the fluorescent part is covalently attached to the polymer. 0 (See S. Sc S Γ 0 Μ ski Li tfl dry 丨 丨 some polymers ib learn 1Z, · 1497 {1 9 9 4) 〇 If you use a coated sample for analysis, you can use the method known in the art U > from other coatings Component extraction polymers. Ethylene cells and monomers with side-m fluorescent functionality can be found in: US 5, 0 43, 406 (Fon ng), S.S 0 S η WS ki et al. Polymerization Physical Science Period i! L, Part A: Polymer Chemistry 3 2: 1 4 9 7 (1 9 9 4) C .L .1 ka 0 et al. F molecule_23 ·· 4 0 8 2 (1 990) Ε. Η. Δ 0 C zar Human Fenhan 2 fi: 5 7 7 2 (1 9 9 3) t Η. A. Fo X et al., Ju Fen 芊 23: 453 3 1 9 9 0) and c * si ai ο η es CU etc. Human poly Λ physical science period fi | 23 ： 20δ9 (19 8 5) 〇 Better ethylenically unsaturated monomer with side-fluorescent fluorescence functionalities including methyl methacrylate, methacrylic acid, forbidden ethylene, SI methacrylic acid 9- Ester 9-methacrylic acid m-2-(9 m -yl) ethyl methacrylate, 1 'M 9-m -yl) ethyl methacrylate, 3-hydroxy-2-methylene-3-1 -Naphthyl) propanoic acid, N-dibenzocycloheptenylpropenamide methacrylic acid (9-phenanthryl) methane and 9-vinylphenanthrene 9-mm acrylic, 3-hydroxy-2-methylene-3-(1-naphthyl) propanoic acid, (9-phenanthryl) methyl methacrylate 9-vinylphenanthrene or its sister 0 Is the chromophore in the polymer a polynuclear aromatic hydrocarbon or a pendant Fluorescently functional ethylenically unsaturated army ♦ All methods are similar. In the radical polymerization process, the f chromophore is treated like another component and is usually added to the monomer at the beginning of the reaction. 1 However, for those who are familiar with this technique (please read the notes on the back before filling this page) This paper size applies to Chinese national standards (CNS > 8 4 grid (210X297 mm) 6 9 1402 455625 A7 B7 V. Description of the Invention (5 Printed by Shellfish Consumer Cooperative of the Central Government of the Ministry of Economic Affairs.圑 or good should be based on a basic raw material of ethyl butyl butyl methyl ethyl pentyl methyl carbamide. On the color * 5, compared with I, the anti-meso-derivative acid, iso, acryl, and decyl are discussed at the end of the amount of ir, and the generation is mono-enoic acid II iso-acid methyl SIIE. Add ^ polyamine acid to the acid system of allylhexene acetate, hexanoic acid, i ^ l-Btba, t ° based materials shop by fetal acid, allyl propionate n-olefin any or the amount of side The 5W isopropyl group, its propylene esters ethyl, allyl, and alkanoic acid propagate in this group. Polyacrylic acid 2-ester propyl ester tetraenyl is soluble in color M to color to line description package, propyl methane acid decamyl should be machine mattress hair JI hair 01 and further description, class And this alkenyl isomethyl, di-n-based, anti-what is W. 0 It is possible to choose a combination of C propionic acid, methyl ester and decadecanoate, which are suitable for the selection of mediators that are based on acid, acid, butene, and pentamer. Acrylic acid, allyl, methyl, propyl, allyl, and allyl ring. Ο Is not used for polymerization but is good for single-group recognition of allyl, such as butyl, ortho-propyl valerate, or habit. It is more color-changing. N-Esteryl alkenyl methyl n-ene denaturation Zhiguang to Ιο-type hair-like methyl encapsulation alkanoic acid hexyl allyl methyl, acid propyl alkane fluorescein and M3 can be regarded as monomethyl or succinate Group, _alkenyl, yiminglian} 1 is related to allyl acid, methorane propionate, etc. ο Outer selects the esters of propyl, allyl, octyl, Cheng Jie's original book is as follows: 0.vft selected I acid acid mono S) ester pentyl ester n-decamethyl ester This property is prepared by the group owner ο Benzene} n-methyl, n-propionate, pentam-1 * A coloring substance for water should be between propyl propyl, this acid ester, n-enoate isocyanate, and it may contain a total amount of anti-M hair. : Alkenyl acrylic acid butyric acid Known for inclusion and poly «00 acetic acid Γ those containing propylene allyl propylene isoprene have been-poly humanoid 0. Zylene C two packs, acid, propyl methyl, acid propyl, etc. All kinds of propenes are used as examples of propenes. Examples are cumene II and ester alkenyl (read the notes on the back before filling in this page) This paper Applicable to Chinese National Standards (CNS). A4 scale (210 × 297 mm) 7 9 1402 455525

A 6 / 1- Explains that allyl methyl pentarate such as allyl methyl esters and allyl ethyl bromide such as 0 acid allyloxy 3 acrylic acid allyl propyl methacrylate Tablet benzyl 2 Allyl allyl isoformate, isopropyl allyl methyl ethoxybutyrate ~ 2 allyl allyl methyl and ester butoxymethyl-2 allyl allyl radical Methyl hydroxy, ester-containing hydroxy I 2 acid allyl group such as body single group fcb has official hydrogenation of active succinate allyl a / 1. · Replacement such as ester acid allyl methyl sulfonate containing ester propyl Ethyl hydroxy-3 acid allyl and ester ethyl methyl phosphate containing allyl and allyl methyl sulfonate and allyl methyl ethyl sulfonate m allyl propylene ethylbenzene 'allyl containing monomer single The others are made of nitrile allyl, benzyl methene, sulfonyl ethene phthalene, ethyl benzyl methyl-α nitrile allyl methenyl pentadienyl ethyl cyanide Propyl chloride, ethyl ethyl butyl n-r0, ethyl ethyl isopropyl ether Ethyl ethylhexyl ethyl isohydroxytris' ether alkenyl ethyl ether alkenyl (read the notes on the back before filling this page) radical fct 3 chain S Jsser ethyl V diyl alcohol in di (V ethyl _ Diene, Diethyl ether diethyl ether two-dimensional fermentation,

Bi ethyl acetoacetate such as quaternary ethyl butyl \ ester ene acetate propylene ethene acetic acid hexamethylene diethylidene vinylene, 2 gas, base ester acrylic ethyl methanoate, hydrogen ester allylic acid, 'butyl ester Isoene, acetoic acid decanoate, and esters. The Central Standards Bureau of the Ministry of Economic Affairs, Consumer Affairs Cooperative, printed ene chloride, 0, butane sulfone ketoamine, N, ketopyryl, ethyl. Benthenyl ethylene, vinyl ethyl fluoride, divinyl, vinyl ethyl fluorophenyl ethyl methyl ketone ketoline azole [{allyl allyl, amine allyl '0 allyl amine allyl mevalonic Dukes' C class alkylene amines Dukes allyl amine Dukes \ J / group and A 3, alkyl carboxylic acid and silicon are not ethylenically unsaturated Shu acetate slfib oxide ί which the TS; isopropyl group, an alkenyl amine oxide sand Niang 、 Alkenyloxypropylsilyl I-based trioxyethylpropyltriyloxybutyranyl S N-allyloxysilyl methyl This paper size is applicable to China National Standard (CNS) A4 (210X 297 male) %) 9 1402 455625 A7 B7 V. Description of the invention 7) Its amidines such as di- and tri-carboxylic acid dialkyl esters and trialkyl esters such as itaconic acid, etc., including di (2-ethylhexyl) maleate, dibutyl maleate, rich Dimethyl malate », dimethyl itaconic acid, diethyl panconate, trimethyl ornithate, diethyl mesanoate, di (2-ethylhexyl) itaconate, itaconic acid Di (2-chloroethyl) ester, maleic acid, maleic anhydride, fumaric acid, itaconic acid; and olefins such as diisobutylene, 1-octene, 1-decene, 1-hexadecene, and the like. These types of monomers are generally carried out in the presence of a water-soluble or oil-soluble starter. Examples of useful starters include: osmium peroxoate, peroxides, hydrogen peroxide, osmium percarbonate, osmium acetate, osmium perbenzoate, azo-functional compounds, and other free radical species. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Surfactants are commonly used in emulsion or liquid separation polymerization to provide stability and control particle size. Conventional surfactants include genistein or non-children emulsifiers or their sisters. Typical anionic emulsification m includes (but is not limited to): alkyl sulfonium or ammonium sulfonium, alkyl ether sulfonium sulfonium or ammonium sulfonium, alkyl aryl ether sulfate sulfonium or ammonium sulfonium, alkyl sulfonate, fatty acid sulfonium, sulfonium Succinate hydrazone, diphenyl ether disulfonate, and complex organic phosphate esters of hydrazones or free acids. Typical nonionic emulsifiers include (but are not limited to): polyethers such as condensates of ethylene oxide and propylene oxide containing straight and branched alkyl groups, and alkylaryl polyethylene glycols and polypropylene Dizyme ethers and thioethers, alkylphenoxy poly (ethoxy) ethenes having alkyl groups containing from about 7 to about 18® carbon atoms and from about 4 to about 100 ethoxy units Ferments and polyoxyene derivatives of hexitol include sorbitol anhydrides, sorbides f, sorbides, mannitans mannitans, and nannides. The surfactant used by the surfactant in the polymer composition of the present invention is the total weight of the final composition. The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) 9 9 1402 4 5 bo 2 5 A7 B7 5 、 Explanation of the invention (large amount of 8 or tincture transfer) Whatever is used to make the polymer condensable photofluorescence brightening. This preparation is suitable for example, including the transfer of the inclusion agent. Quantum division control M The properties of alkane or alkane or alkane% of thioalkane-like thioalkane or alkane in eyebrow polymerization are used to aggregate a large amount of intermediates into hydrocarbon-like halides or β-alkanes.量 至 ο ^ Quantum fractions are converged to increase and use! One can 2 and sometimes including its additions from 0 can be mono- and mono-ethylenic position and poly-ethylenic Deer, difermentate, difermentate, ethanedionate, triethylenepropionate, polymethacrylate, methacrylic acid, dimethylpropionate: methyl containing dimethylformate, dimethyl ester, difermentate This diacid is polyethylenic acid. Alkenyl allyl methyl, dimethyl body, di beta alcohol, dipentanoic acid, allyl formate, allyl propylene, ester alcohol, disuccinate, allyl tri 'ester, ethyl methytriate, allyl methyl , Tetravalic acid dipentarate diallylic acid allyl pentaerythritol dipentaric acid dipentarate diallyl pentaerythritol tetrapentarate diacrylic acid allyl tetra 'erythritol tetrapentaerythion dipropionate maleic acid, phthalate isopropyl, allyl dipropylene Acid alkyl bridge dichloric acid, phthalate esters, allyl allyl dicarboxylic acid Kangqiaoyi chlorine,, esters_propanolene (please read the notes on the back * before filling this page) Central Ministry of Economic Affairs Printed by Bureau of Work Consumer Cooperatives 6 Tri », ί1 acid allyl allyl dimethyl, tricoll, allyl enol trisuccinic acid succinic acid 3 benzene 1, meta-acid 'allyl allylic allyl dimethyl Acids, cyanoisols, diesters, hexamethylpropyltrimethylene allyltris, propylmethyol 0 dimalonic acid allyls are polymerized in this compound. Propyl A > Cool Material wt cents 10% to the best 01 any 0. The weight of the most important thing is the combination of hair and hair, which is used for the content of the package to make the middle agent foaming, moisturizing agent. , Dose fixation and solidification, Dose bactericidal powder,, Uniform oxygen filling, Resistant absorption This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 2SI7 mm) 91402 455625 A7 B7 5. Description of the invention (9) The coating composition of the present invention can be used to provide a coating on a suitable substrate, such as wood and recycled wood products, concrete, asphalt, fiber cement, stone, marble, clay, plastic (such as polystyrene , Polyethylene, ABS, polyurethane, polyethylene terephthalate, polybutylene terephthalate, polypropylene, polyphenylene, polycarbonate, polyacrylate, polyethylene, No``yl® ) And polymer mills), paper, cardboard, fabrics, leather and gold tinctures (锇 and non-ferrous). It has been unexpectedly found that the inclusion of the fluorescent polymer of the present invention in a coating composition can produce a coating on the resulting coating. Enhanced (IV permanence). Therefore, the coating composition of the present invention is preferably used to coat substrates that need to be routinely exposed to UV light (such as outdoor applications). The coating composition of the present invention can be applied by conventional coating Cloth technology applied to the required substrate, Conventional or airless spray method, roll coating method, brush coating method, curtain shower method, overflow method and dip coating method. When coating on the substrate, the coating composition can be cured at normal temperature or elevated temperature. Method Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative Co., Ltd.-using a 3 mil (0.076 mm) Bird® thin 瞑 pickle applicator to draw a film of each test paint on a 5C drawing. The film was allowed to dry for 7 days at 25C and 50% relative humidity. The initial gloss readings of 20 ° and 60 ° were taken using a GUSsgard® II gloss meter (light reflection at 20 ° and 60 ° from vertical). In Veathe "- 〇-meter® after exposure, repeatedly take 20 ° and 60 ° gloss and record or percentage retention from the initial value. Loss of gloss is a indicator of poor longevity; therefore, the higher the percentage retention, the longer the shot duration. Good. Adhesive Resistance-Use 3 mils (0.076 mm) of Bi "d® film cell paper. Applicable to Chinese Standard (CNS) A4 (210XW7 mm > 9 1402) (Please read the back Note for this page, please fill out this page) 11 4 5 56 2 5 A7 B7 V. Description of the invention (1 〇) Applicator On aluminum "Q" board (Alodine® 1200S), paint the thin layers of each test paint. Allow the film to dry for 7 days at 25T: and 50% relative humidity, and then expose after VE Veather-0-Beter · ® Measure the Y reflectivity of the paint film with a reflectometer. Then contaminate the board with hafnium oxide slurry (250 g of water, 2 drops of anionic separating agent, 125 g of hafnium oxide, fully dispersed), and in the air Dry for 3 hours and dry in the oven for 1 hour. The board is cooled to room temperature. The paint film is washed with tap cloth under running water and dried in air for 4 hours. The reflectance meter was used to measure the Y-reflectivity of the contaminated area and it was recorded as a percentage of the original radon number. The higher the percentage retention, the cleaner the paint film, and the better the durability. The following examples are given to further illustrate the various objects of the present invention, but are not intended to limit the scope of the present invention in any way. The following abbreviations are used throughout the examples. ΑΑ = MMA of acrylic acid = methacrylic acid methacrylate βA = butyl deer methacrylate Sty = stupid ethylene BMA = butyl deer methacrylate AnMA = 9-methyl acrylate ΑΑ = ethyl acrylate ΝΜΑ = methacrylic acid I-forbidden Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Industrial and Consumer Cooperatives HA Α = methacrylic acid Example 1: Preparation of acrylic latex from 9-methacrylic acid methacrylate Composition: 47ΒΑ / 52ΜΗΑ / 1 ΑηΜΑ equipped with mechanical paddle Polymerization was performed in a 1-liter four-necked round-bottom glass bottle with a stirrer, a thermocouple to track the temperature, a reflux condenser, and a heating and cooling and nitrogen-filling device. 200 g of deionized water and 0.5 g of sodium dodecylbenzyl sulfonate were charged into the bottle, and then heated to 851. 90 grams of deionized water and 0.5 grams of twelve paper sizes are applicable to China National Standard (CNS) A4 specifications (210X297 mm) 9 1402 (read the notes on the back first and then fill out this page) 12 455625 A7 B7 5 2. Description of the invention (11) Sodium alkylbenzenesulfonate, 118 g of butyl acrylate, 130 g of methyl methacrylate, and 2.5 g of 9-metyl methacrylate were used to prepare a monomer pre-emulsion. This pre-emulsion (12.5 g) was added to the bottle. Next, 0.75 g of ammonium persulfate (APS) dissolved in 5 g of water was added. After 15 minutes, M began feeding linearly the remaining pre-emulsion and 0.4 g of APS in 75 g of deionized water in 2.5 hours. If the box is required, heating and cooling are applied, and K keeps the reaction temperature at 85t :. When the addition is complete, wash the pre-emulsion container into the bottle with 30 grams of deionized water. After 30 minutes, the bottle was cooled to 60 ° F, and 0.003 g of FeS〇4 • 7Η2 ·· 1.5 g of a 70% aqueous solution of third butyl hydroperoxide and 0.9 g of sodium formaldehyde sulfoxylate were added to the bottle admixture in a total of 33.5 Grams of aqueous solution in deionized water. The reaction mixture was allowed to cool to room temperature and passed «. A polymer latex was obtained with a solid content of 41.0 weight reed (outside of w t), a particle size of 8 3 n a, and ρ. 2.5. This polymer emits pretty light at 4 1 3 n m (ex364nn). Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Example 2: Preparation of acrylic latex composed of methacrylic acid 1-ethyl acrylate: 47BAA / 52. 1 ΜΗΑ / 0. 9ΝΕΜ Follow the procedure of Example 1, but 90 grams of deionized Water, 0.5 g of sodium dodecylbenzenesulfonate, 118 g of butyl acrylate, 130 g of methyl methacrylate, and 2.3 g of forbidden ethyl methacrylate were used to prepare a monomer pre-emulsion. A polymer latex was obtained having a solid content of 4 1.4 w t〆, a particle size of 103 n m, and r > Η 2.3. This polymer emits fluorescence at 3 40 η * (ex 28 0nm).

Example 3: Preparation of stupid vinyl acrylic latex with 9-methyl methacrylate: 50BA / 49Sty / lAnMA Follow the procedure of Example 1, but with 90 g of deionized water and 0.5 g of sodium dodecylbenzylsulfonate , 125 grams of butyl acrylate, 122.5 grams of styrene, and 2.3 grams of this paper are suitable for China National Standards (CNS > Α4ΛGrid (2 丨 0 · 〆29? Mm) 9 1402 (Please read the back Note: Please fill in this page again.) 13 455625 A7 _B7__ V. Description of the invention (12) 9-methacrylic acid to prepare monomer pre-emulsion. At the end of the reaction, 0.003 g of FeS〇4 * 7Η2. 2 · 5 g of Tributyl hydroperoxide and 1.5 g of sodium formaldehyde hypoarsinate in a total of 54.5 g of deionized water were obtained as an aqueous solution. A polymer latex having a solid content of 34.84, a particle size of 91 ^ and? 丨 2.2 was obtained. 1 3 η π (e X 3 6 5 η β > emits fluorescence. Example 4: Preparation of styrene acrylic latex from 1-naphthyl methacrylate Composition: 50BA / 49.lSty / 0.9HEMA Follow Example 1 Procedure, but with 90 grams of deionized water, 0.5 grams of sodium dodecylbenzenesulfonate, 125 grams of butyl acrylate, 123 grams of styrene, and 2.3 grams A monomer pre-emulsion was prepared from naphthyl methacrylate. A polymer latex was obtained with a solid content of 40.5 wt β, a particle size of 8 6 nb, and p Η 2.2. The polymer was found at 3 4 0 nb (e X 2 80 nia) emits fluorescence. Example 5: Preparation of acrylic latex molybdenum from 9-methyl methacrylate: 99 ΕΑ / 1 ΑπΜΑ Follow the procedure of Example 1, but with 90 grams of deionized water, 0.5 grams of ten A pre-emulsion was prepared from sodium dialkylbenzenesulfonate, 247.5 g of ethyl acrylate, and 2.5 g of 9-naphthyl methacrylate. The polymer latex was obtained and its solid content was 40. Printed by the Consumers' Cooperatives of the China Prospective Bureau of the Ministry of Economic Affairs袈, granules 87nn and ρΗ2 · 7. This polymer emits quite at 413nm (ex 3 6 4 nm)

Light D Example 6: Preparation of acrylic latex Composition: 100BHA // 1. Follow the procedure of Example 1, but consist of 250 g of butyl methacrylate and 2.5 g of green onion (which is stirred at the same time until it is almost dissolved), 90 g A monomer pre-emulsion was prepared with deionized water and 0.5 g of sodium dodecylbenzenesulfonate. Obtain the size of the polymer milk paper. Applicable to China National Sample (CNS) A4 condition (2 丨 0 > < 297 mm) 9 1402 (Please read the precautions on the back before filling this page) 14 45 56 2 5 A7 B7 V. Description of the invention (13) Glue, its solid content is 40.6wt 涔, particle size is 112nm and pH is 1.9. This polymer emits strong light at 426nm (ex 364nai). Example 7: Preparation of acrylic latex with Μ suspension: 55BΛ / 43. 5 ΜΗΑ / 1.5. ΑΑ // 1.0. On an equipped paddle stirrer, thermocouple to track temperature, reflux condenser, heating and cooling Polymerization was carried out in a 3-liter four-necked round-bottom glass bottle with nitrogen filling equipment. The bottle was fed with 580 grams of deionized water, 5.3 grams of alkylphenol ethoxylate ammonium sulfate surfactant (AAESS) 60 reai, and 4.0 grams of sodium carbonate, followed by heating to 8 5 t. From 5 50 grams of butyl acrylate-4 3 5 grams of methacrylic acid _, 15 grams of methacrylic acid and 10 grams of Zhao (simultaneously stir until the rest is almost dissolved) Du Yinju And 252.5 g of deionized water, 17 g / ££ 5,560 and 1.0 g of sodium lauryl sulfate to prepare a monomer pre-emulsion. This pre-emulsion (55 grams) was added to the bottle, followed by 3.0 grams of APS which had been dissolved in 17 grams of water. After 15 minutes, K 3.0 hours began to feed the hydrating pre-emulsion and 1.5 grams of APS dissolved in 90 grams of deionized water. If necessary, heating and cooling are applied, and K keeps the reaction temperature at 83 t. When the addition is complete, wash the container of the pre-emulsion with 35 g of deionized water into the bottle. After 30 minutes, the bottle was cooled to 651, and 0.012 g of FeS〇4 · 7H20, 0.012 g of ethylene diamine tetraacetic acid tetranaphthalene, 4.0 g of 70 mM tert-butyl hydroperoxide aqueous solution, and 2.0 g of isopropyl were added to the bottle. An aqueous solution of ascorbic acid in a total of 132 grams of deionized water was used to raise the pH with 6.7 grams of 28% ammonium hydroxide. The reaction mixture was cooled to room temperature and filtered to obtain a polymer latex having a solid content of 46.7 wt, a particle size of 130 η ·, and a pH of 6.fi. This polymer emits fluorescence at 422nn (ex 364η ·). Use a gel permeation chromatography (GPC) with UV detector and refractive index detector in front and back to determine the fluorescent part. The paper size is in accordance with the Chinese National Standard (CNS) 8 and 4 (210 X 297 mm). ) 9 1402 (Please read the notes on the back before filling out this page) 15 455625 A7 B7 V. Description of the invention (14) Whether it is covalently connected to the polymer 鐽. Example 8: Preparation of acrylic latex with Xue ·· 55BA / 43. 5HMA / 1. 5HAA // 0. Follow the procedure of Example 7, but use 5 grams of pre-emulsion, and at the end of the polymerization, use An aqueous solution of 2.0 g of tert-butyl hydrogenated gas and 1.0 g of isoascorbic acid in a total of 68 g of deionized water was added. A polymer latex was obtained having a solid content of 48.9 wt, a particle size of 1 2 6 η π, and p Η 8.7. This polymer emits strong light at 422nin (ex 364nm). Example 9 (comparative example): Preparation of conventional acrylic latex

m fig, ： 55B A / 43. 5MMA / 1. 5ΗΛ A Following the procedure of Example 7, but with 175 grams of deionized water, 17 grams of AAESS60 light ai, 550 grams of butyl acrylate, 4 3 5 grams of methyl methacrylate And 15 grams of methacrylic acid to prepare a pre-emulsion. And at the end of the polymerization reaction, 0.006 g of FeS〇4 * 7Hs0, 0.006 g of ethylene diamine tetraacetic acid tetranaphthalene, 1.0 g of 70-tributyl hydrogen peroxide aqueous solution, and 0.5 g of isoascorbic acid were added in a total of 35 g to Aqueous solution in ionized water. A polymer latex was obtained, having a solid content of > 2.2 wt%, a particle size of 124η ·, and a pH of 9.6. The polymer did not exhibit fluorescence. Printed by the Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs Example 10: Preparation of dumb Ethylene-acrylic latex mb £: 50BA / 46Sty / 4.0MAA // 0.5 ^ On a 3-liter four-neck with a paddle stirrer, a thermocouple to track temperature, a reflux condenser, heating and cooling, and nitrogen cooking Polymerization was carried out in a round-bottom glass bottle. 400 g of deionized water was fed into the bottle, and then heated to 8310. Between 41.5 g of deionized water and 3.5 g of ammonium persulfate dissolved in 12 g of deionized water and 18 g (solid basis) 60 ηπι seed crystal latex. 500 g propylene paper bearing standard applies China National Standard (CNS) A4 specification (210X297 mm) 9 1402 (Please read the precautions on the back before filling this page) 16 45 56 2 5 A7 B7 V. Description of the invention (15) (Please read the notes on the back before filling this page) Butyl methacrylate, 460 g of styrene, 40 g of methacrylic acid and 5 g of rest (while stirring until Rest and dissolving) and 2 9 5 grams of deionized water, 8 5 grams Λ AESS 3 5 5 a and 3.2 grams Sodium lauryl sulfonate is used to prepare monomer pre-emulsion. Add the military pre-emulsion and 90 g of deionized water containing 1.2 g of ammonium persulfate to the bottle over 3 hours. If necessary, apply heating and cooling. The reaction temperature was maintained at 8 3 t. When the addition was completed, the container of the pre-emulsion was washed with 25 g of deionized water and washed into the reaction bottle. After 30 minutes, the bottle was cooled to 651, and 0.01 g of the solution was added to the bottle. FeS〇4 · 7、20, 2,0 g of 70 涔 aqueous solution of third butyl hydrogen peroxide and 1.0 g of erythorbic acid in a total of 46 g of deionized water. The reaction mixture was cooled to room temperature and filtered. Polymerization was obtained Polymer latex with a solid content of 52.7 wt., A particle size of 2 1 6 η *, and ρ Η 2.5. This polymer emits pretty light at 4 1 8 nm (e X 364η ·). Example 11: Preparation and Evaluation of semi-gloss paints The latex polymers of Examples 7, 8 and 9 were formulated into semi-gloss paints, which were evaluated before and after accelerated weathering. The formulas of the paints are shown in Table I and the properties of the coatings are shown in the table. II. Employees' Cooperatives, Ben Ben 9 1402, Central Standards Bureau, Ministry of Economic Affairs # 准 （CNS） 4 specifications (210X297 mm) 455625 A7 B7 _ V. Description of the invention (16) Table _.. 1 ·· 2 4 P V C paint formula (all fleas burned in Beijing)

Ingredients Paint A Paint B Paint C Water anionic dispersant Non «child wet elixir hydroxyethyl cellulose (2.5 涔) Defoamer Rutile T i 0 2 7 2 72 72 .0 50 50 50 Please read the notes before you fill in%. This page 264 264.7 2 6 4. Latex 7 Latex 8 Latex 9 Antifoam Nonionic Wetting Tincture 5 18 49 4 463.6 Nonionic Thickening Agent (20) 15 15, 15. Su Wei 0, Ji Bing 7 7 2 Consumption cooperation between employees of the Central Bureau of Standards, Ministry of Economic Affairs, Du printed water, 0 Biophysical micro-resistance comparison, which is used to evaluate ae, long-wearable outer film, aew in paint The evolution of the old film thin S plus 0 Γ Γ e 0 Exposure © Γ 0 After exposure to light, the time is small Γ e Exposure (Θ factory paper scales apply Chinese National Standard (CNS) Λ4 specifications ( 210X297 mm) 18 9 1402 A7 B7 V. Description of the invention (17) The adhesion of the dirt was measured after 408 hours of exposure. The results are described in Table I below.

Paint A

Paint B Initial gloss 20 ° Gloss 31 16 16 60 ° Gloss 67 59 56 Gloss retention 20 ° Gloss 110 98 60 60 ° Gloss 116 10 1 89 Resistance to adhesion 89 Know 7 1 舛 (please first (Please read the notes on the back and fill in this page again.) A comparative example printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The above data shows that each of the paints A and B containing the connected open base part is more than the paint without open part. C exhibits improved external durability. Example 12: Evaluation of the chromophore moiety bound to the polymer A polymer sample prepared during the polymerization and the polymer sample added during the post-polymerization were analyzed by phase-feeding HPLC. The main polymer composition was 41.2BΛ / 57.5MMA / 1.3ΜΑΛ. The samples were diluted 1:10 with formazan and shaken for 2 hours. The diluted product was centrifuged at 45,000 rpm for 15 minutes and the supernatant was analyzed. (If the sample amount is outside the calibration range M, the dilute product can be further diluted as needed). Perkin-Elmer® series 4HPLC with Supelco® LC-18-DB column (25caix 4ma) was used for analysis with acetonitrile / water (95/5) mobile phase and flow rate IbL / diU. M250 wood paper scale is applicable to China National Standard (CMS) A4 specification (210 X 297 cm) 19 9 1402 4 5 5 6 2 5 A7 B7 V. Description of the invention (18) nra excitation wavelength and fluorescence detection wavelength of 398nm Detect fluorescence. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

Sample 2 3 4 Μ is added. After anti-gathering, the period should be anti-gathering. (Please read the precautions on the back before filling out this page.) I. The standard is -mill Μ Di liquid emulsion Μ

. • ST The standard of this paper is applicable to Chinese National Standard (CNS) Λ4 gauge (210 × 297 cm) 20 91402

Claims (1)

Amendment to the scope of patent application (January 15, 1989) Sex shop b The SZ issued 8% of κ base or W sex Α Λ ^ ν Λ ί 1. It makes Γ Tu Ying included 1 includes ο contains .ο The combination of the physical method and the total amount of the total amount of the combined object account for its sex; the photo-synthetic egg is mono-prepared and the co-saturated species are not homogenous and the photofluorine group (group C, lower naphthalene from Two alternatives, pyrazolene and phenanthrene 0 phenanthrene fluorescein Π Θ S phenanthrene y benzene phenanthrene is aromatically substituted by the phyto-derivatives from the family of agglomerative photofluorescence-resistant long-lasting VU compounds Tu Qiang Zengfu 1 2 of 6 & total weight single deposit in the storage * 4r and body single and unsaturated ethylenic to synthetic fluorescent fluorescent naphthalene Dense: Benzene group, Zuwanlie, lower naphthalene optional inlay system, oxacarbidine, 0 fluorene, phenanthrene and aromatic derivatives, and naphthalene; acidic allene, i B Allyl Methanoate-9 Allyl Methanoate Allyl Methyl Ethyl Acetate— / Glyoxymethyl 2 Acetyl, Propyl Methyl Naphthalene, Ethyl Allyl Ethyl Hydroxy-3 R Ester Ethyl Ethyl Acetate— / Base 0 Employee Benefits of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the committee. Chimethylene-2 I-allyl allyl heptyl and benzene di IN, acid propyl ban I 1 / f \ chemical light. Fluorene phenanthrene, ethyl-9- and polyester Jiaguang 丨 Item of Firefly 9 (2 Acid Dipropenyl Fanki Li Jiazhuan, please apply for the application such as 3 and its 0, Fluorine Λ phenanthrene, naphthalene group τ ΉΤΤ selectable compounds allyl acid allyl , Allyl methyl naphthyl acetate and bio-derived aromatic aromatic radical methylidene-2 I hydroxy I 30 propyl propyl methyl r acid Λ 1 / yl naphthalene 113 S methyl β 3?-9 / | \ Acid alkenyl ethene and phenanthrene and this paper size are applicable to China National Standards (CNS) A4 (210 × 297) ^ ΓΓ7 < ^ b \ ^ X9trj ^^ Above ¥ Q4 A4 C4 455625 (Year / Month / _TH Shao Ming-4 ^ = 5 = 5¾¾ New patent specification Chinese invention new name English name Nationality Fluorescent polymer and its preparation method FLUORESCENT POLYMERS AND A METHOD OF PREPARING ΤΉΕ SAME Patricia · Mali · Rice Cosplay Inventor and Residence Name (Name) United States United States • Pennsylvania * Oss Village • Rohm and Haas Company 191 Hongling Road 191 Ding, Member of the Central Government Bureau of the Ministry of Economic Affairs, 2 Consumer Cooperatives, India Policy 3, Applicant's Nationality Residence 'Residence (Office) Representative Name American Art Painting • Pennsylvania * Felder Feia City • 100 Independence Avenue West District Marco S · Adair Coffee scale free use _ furniture C such as Jingmen Ji Qing) 91402 Amendment to the scope of patent application (January 15, 1989) Sex shop b The SZ issued 8% of κ base or W sex Α Λ ^ ν Λ ί 1. It makes Γ Tu Ying included 1 includes ο contains .ο The combination of the physical method and the total amount of the total amount of the combined object account for its sex; the photo-synthetic egg is mono-prepared and the co-saturated species are not homogenous and the photofluorine group (group C, lower naphthalene from Two alternatives, pyrazolene and phenanthrene 0 phenanthrene fluorescein Π Θ S phenanthrene y benzene phenanthrene is aromatically substituted by the phyto-derivatives from the family of agglomerative photofluorescence-resistant long-lasting VU compounds Tu Qiang Zengfu 1 2 of 6 & total weight single deposit in the storage * 4r and body single and unsaturated ethylenic to synthetic fluorescent fluorescent naphthalene Dense: Benzene group, Zuwanlie, lower naphthalene optional inlay system, oxacarbidine, 0 fluorene, phenanthrene and aromatic derivatives, and naphthalene; acidic allene, i B Allyl Methanoate-9 Allyl Methanoate Allyl Methyl Ethyl Acetate— / Glyoxymethyl 2 Acetyl, Propyl Methyl Naphthalene, Ethyl Allyl Ethyl Hydroxy-3 R Ester Ethyl Ethyl Acetate— / Base 0 Employee Benefits of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the committee. Chimethylene-2 I-allyl allyl heptyl and benzene di IN, acid propyl ban I 1 / f \ chemical light. Fluorene phenanthrene, ethyl-9- and polyester Jiaguang 丨 Item of Firefly 9 (2 Acid Dipropenyl Fanki Li Jiazhuan, please apply for the application such as 3 and its 0, Fluorine Λ phenanthrene, naphthalene group τ ΉΤΤ selectable compounds allyl acid allyl , Allyl methyl naphthyl acetate and bio-derived aromatic aromatic radical methylidene-2 I hydroxy I 30 propyl propyl methyl r acid Λ 1 / yl naphthalene 113 S methyl β 3?-9 / | \ Acid alkenyl ethene and phenanthrene and this paper size are applicable to China National Standards (CNS) A4 (210 × 297)